Process for starilizing acid liquor



Patented Aug. 6, 1935 airs , 2,010,337 rnoonss roa s'rAerLrzrNG ACID mason Adrianus Johannes van ?eski, Amsterdam, Netherlands, assignor to Shell Development Company, San Francisco, Calif.

No Drawing.

Application July 21, 1932, Serial No. 623,904. In the Netherlands July 25, 1931 12 Claims.

It has already been proposed to eiiect the absorption of olefines in strong acids, such assulphuric acid, phosphoric acid, chlorosulphonic filed May 20, 1930; U. S. Patent 1,948,891 issued February 27, 1934, U. S. Patent 1,958,578 issued May 15, 1934, and U. S. application Ser. No. 608,872; filed May 2nd, 1932. In many cases it appeared that besides this desired efiect the forrnation of undesired unsaturated products, in consequence ofthe polymerization of the products or of the olefines themselves, was obviated, which must be ascribed to the polymerization-hindering capacity of the adsorption-promoting substances.

' It has now been found that the polymerizationhindering capacity of these substances can be utilized not only during the absorption of the olefines but also in those cases where besides free strong acids (such as sulphuric acid, phosphoric acid, chlorosulphonic acid, strong sulphonic acids, etc.) alcohols, olefines, alkyland/ or dialkyl compounds of the-strong acids or other polymerizable compounds are present. Consequently the process according to the invention consists in the addition to or the formation in these mixtures of substances hindering the polymerization of the compounds contacted with the free strong acids.

Thus, for instance, according to the invention use is made of one or more, hydrous or anhydrous, complex metallic cyanides and/ or compounds the chemical formula of which can be derived from these cyanides, e. g. ferrihydrocyanic acid, ferrohydrocyanic acid, or salts of these acids. It is also possible to use one or more compounds of hydrocarbons with one or more double carbon bonds in the molecule, such as propylene, normal butylene, isobutylene, tri-methyl ethylene, diamylene, 'isoprene, cyclohexene, pinene, with complex metallic cyanides, such as potassium ferrocyanides, ferrohydrocyanic acid or ferrihydrocyanic acid.

According to another embodiment of the process according to the invention one or more metals of the platinum group or compounds thereof are used in a finely divided condition and preferably 'on a carrier, e. g. PtCh on carbon black, rhodium black, etc.

Still another embodiment of the process according to the invention resides inthe use of soluble compounds of the metals of the platinum group of copper, iron, cobalt, nickel or silver, for instance cuprocyanide. If desired soluble complex compounds can be formed in the acid liquid by converting in this liquid soluble (such as cuprocyanide) or insoluble (such as potassium platinochloride) non-complex compounds of these metals with the aid of carbon monoxide, nitrogen oxide or ethylene.

In all these cases the mixtures can be stored during a longer time and at higher temperatures than in the absence of the relative polymerization-hindering substances.

The addition to or the production in the mixtures of substances hindering the polymerization of the compounds with the free strong acids can be applied in many instances. Thus, for example, in order to stabilize the products obtained by the absorption of olefines in a strong acid in the absence of polymerization-hindering sub stances, it is possible to add such substances afterwards. I

Also in those cases where a mixture of alkylated acid and strong acid has to undergo a not sufliciently rapid reaction with a third substance,

it can be brought about by the addition of polymerization-hindering substances that the alkyl acid originally present remains present until the end of] the reaction, instead of being converted into useless polymers.

Furthermore polymerization-hinderingsubstances can be added also to mixtures of alcohols,

strong acid and substances which have to interact with the alcohols under the influence of the strong acid.

Moreover the polymerization-hindering capacity can be turned to account in those cases where strong acid is gradually added to a reaction mixture containing olefines, e. g. a mixture of olefines and phenols (or aromatic sulphonic acids), in order to bring about an interaction between the olefmes and one or more of .the other components.

t goes without saying that besides those mentioned above many other modes of applying the process are conceivable, likewise falling within the scope of the invention.

Example I In a solution containing 30.6 grams secondary butyl sulphuric acid 10.6 grams sulphuric acid and 10.9 grams water, all the secondary butyl sulphuric acid present has been converted after hours at 20 0. into unsaturated butylene polymers, whilst no alcohols could be obtained from the mixture by applying the known hydrolysis.

Upon 3 grams of K4Fe(CN)e3l-I2O being added to the same original solution, only 14% of the butyl Sulphuric acid were polymerized under other Wise identical conditions whilst after hydrolysis I l grams of butyl alcohol could be obtainedfrom the non-polymerized product.

Example II ing in total to 8.7 grams.

Upon 3 grams of cuprocyanide being dissolved in the same original solution only 0.3 gram was polymerized under otherwise identical conditions,

whilst after hydrolysis 13.8 grams of butyl alco hol was obtained from the non-polymerized product.

The expression acid liquor as used throughout the specification and claims is intended to embrace acid solutions (true or colloidal) of alcohols, olefines and alkyl acid esters, dialkyl esters and neutral esters of strong acids, and

similar polymerizable compounds wherein the acid medium is a free strong acid as sulfuric acid, phosphoric acid, chlorosulfonic acid, the sulfonic acids and the like. 4 e

What I claim is: Y W V l. A process for stabilizing preformed acid liquor which comprises adding thereto'after its formation at least one member of "the; group consisting of compounds of iron, cobalt and nickel and of elements and compounds of the metals v of the platinum group.

2. A process for stabilizing preformed acid liquor which comprises adding thereto after its formation at least one member of the group consisting of compounds of copper and silver.

3. A process for stabilizing preformed acid liquor which comprises adding thereto after its formation at least one member of the group consisting of soluble compounds of the metals of the platinum group, of iron, cobalt and nickel.

4. A process for stabilizing preformed acid liquor which comprises adding thereto after its formation at least one member of the group consisting of soluble compounds of copper and. silver.

5. A process'for stabilizing preformed acid liquor which comprises adding thereto after its formation a soluble cyano compound of a metal of the group consisting of metals of the platinum 7 group, iron, cobalt and nickel.

6. A process for-stabilizing preformed acid liquor which comprises adding thereto after its formationasoluble cyano compound of a metal of the group consisting of copper andsilven- 7. A process for stabilizing preformed acid liquor which comprises adding thereto after its formation a soluble complex metallo compound obtained by the reaction of a non-complex compound of a metal of the group consisting of metals 'of'thc platinum group, iron, cobalt and nickel, with carbon monoxide.

8. A process for stabilizing;v preformed acid liquor which comprises adding thereto'after its formation ,a'soluble complex metallo compound obtained by the reaction of a non-complex compound of a metal of the group consisting of met als of the platinum with nitric oxides w 1 9. A process for stabilizing preformed acid liquor whichcomprises adding thereto after its group,iron, cobalt and nickel,

formation a solubleicomplex metallo compound obtained by the reaction of 1a nonecomplex come pound of a metal of :the group consisting ofm etals of the platinum group; iron, cobalt and-nickel,

with ethylene.

10. A process for. stabilizing preformed acid" liquorwhich comprises adding thereto after its formation asoluble complex mctallo'compound" obtained by the reaction of a non-complex compound of a metal of the group consisting of copper and silver with carbon monoxide.

7 11. A process for stabilizing preformed acid.. liquor which comprises adding thereto after its formation a soluble complex metallo compound obtained by the reaction ofanon-complex com pound of a metal of the group consisting of copper and silver with nitric oxide.

12. A processfor stabilizing preformed acid liquor which comprises adding thereto after its formation a soluble complex metallo compound obtained by, the reaction of a. non-complex'com-- pound of a. metal of the group consisting f per and silver with ethylene.

ADRIANUSJOHANNES vm PESKI. 

